Isothiazoleazo hydroxypyridone dyes

ABSTRACT

Isothiazole dyes of the formula ##STR1## where X is substituted or unsubstituted C 1  -C 8  -alkyl or substituted or unsubstituted phenyl, 
     Y is hydrogen, cyano, chlorine or bromine, 
     R 1  is hydrogen, C 1  -C 4  -alkyl or phenyl, 
     R 2  is hydrogen, cyano, carbamoyl, C 1  -C 4  -monoalkyl- or -dialkyl-carbamoyl, C 1  -C 6  -alkanoyl, C 1  -C 6  -alkoxycarbonyl or 2-(C 1  -C 4  -alkoxy)-ethoxycarbonyl and 
     R 3  is hydrogen, C 1  -C 8  -alkyl which may be substituted and/or interrupted by one or two oxygen atoms, or is C 5  -C 7  -cycloalkyl, C 3  -C 6  -alkenyl or phenyl, are useful for dyeing synthetic fibers.

The present invention relates to novel isothiazoleazo dyes incorporatinga 5-aminoisothiazole derivative as diazo component and a6-hydroxypyrid-2-one derivative as coupling component, and to the usethereof for dyeing synthetic fibers.

DE-A-3,433,958 has already disclosed isothiazoleazo dyes incorporating3-methyl-4-nitro-5-aminoisothiazole as diazo component.

It is an object of the present invention to provide novel nitro-freeisothiazoleazo dyes having advantageous application properties.

We have found that this object is achieved with isothiazoleazo dyes ofthe formula I ##STR2## where X is substituted or unsubstituted C₁ -C₈-alkyl or substituted or unsubstituted phenyl,

Y is hydrogen, cyano, chlorine or bromine,

R¹ is hydrogen, C₁ -C₄ -alkyl or phenyl,

R² is hydrogen, cyano, carbamoyl, C₁ -C₄ -monoalkyl- or-dialkyl-carbamoyl, C₁ -C₆ -alkanoyl, C₁ -C₆ -alkoxycarbonyl or 2-(C₁-C₄ -alkoxy)

ethoxycarbonyl and

R³ is hydrogen, C₁ -C₈ -alkyl which may be substituted and/orinterrupted by one or two oxygen atoms, or is C₅ -C₇ -cycloalkyl, C₃ -C₆-alkenyl or phenyl.

All the alkyl groups appearing in the abovementioned radicals can be notonly straight-chain but also branched.

If X is substituted C₁ -C₈ -alkyl, suitable substituents are for examplechlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₄-alkoxycarbonyl or unsubstituted or substituted C₁ -C₄ -alkyl-, C₁ -C₄-alkoxy-, chlorine-, bromine- or cyano-substituted phenyl.

If X is substituted phenyl, suitable substituents are for example C₁ -C₄-alkyl, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, chlorine, bromine, C₁ -C₄-alkoxycarbonyl, cyano or C₁ -C₄ -dialkylaminosulphonyl.

If R³ is substituted C₁ -C₈ -alkyl which may be interrupted by one ortwo oxygen atoms, suitable substituents are for example phenyl, cyano,C₁ -C₈ -alkoxycarbonyl, phenoxycarbonyl, halogen, in particular chlorineor bromine, hydroxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, C₅ -C₇-cycloalkoxy or phenoxy.

X, R¹ and R³ are each for example methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl or tertbutyl.

X and R³ are each further for example pentyl, isopentyl, neopentyl,tert-pentyl, hexyl, heptyl, octyl or 2-ethylhexyl.

X is further for example 2-chloroethyl, 2-bromoethyl, cyanomethyl,2-cyanoethyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-methoxyethyl,2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, benzyl, 1- or 2-phenylethyl, o-, m- orp-methylbenzyl, o-, m- or p-bromobenzyl, o-, m- or p-chlorobenzyl, o-,m- or p-methoxybenzyl, o-, m- or p-ethoxybenzyl, o-, m- orp-cyanobenzyl, phenyl, o-, m- or p-methylphenyl, o-, m- orp-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-chlorophenyl, o-,m- or p-bromophenyl, o-, m- or p-hydroxyphenyl, p-phenoxyphenyl, o-, m-or p-cyanophenyl, p-dimethylaminosulfonylphenyl orp-diethylaminosulfonylphenyl.

Further specific examples of R³ are 2-methoxyethyl, 2-ethoxyethyl,2-propoxyethyl, 2-butoxyethyl, 2-methoxypropyl, 3-methoxypropyl,3-ethoxypropyl, 2-methoxybutyl, 4-methoxybutyl, 2-ethoxybutyl,4-ethoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, benzyl, 1- or2-phenylethyl, 8-phenyl-4,7-dioxaoctyl, 2-cyanoethyl, 3-cyanopropyl,4-cyanobutyl, 5-cyano-3-oxapentyl, 6-cyano-4-oxahexyl,8-cyano-4-oxahexyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl,2,3-dihydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl,5-hydroxy-3-oxapentyl, 6-hydroxy-4-oxahexyl, 8-hydroxy-4-oxaoctyl,8-hydroxy-3,6dioxaoctyl, 2-phenyl-2-hydroxyethyl, 2-chloroethyl,2-bromoethyl, 2-phenoxyethyl, 3-phenoxypropyl, 4-phenoxybutyl,5-phenoxy-3-oxapentyl, 6-phenoxy-4-oxahexyl, 8-phenoxy-4-oxaoctyl,2-cyclohexyloxyethyl, 3-cyclohexyloxypropyl, 4-cyclohexyloxybutyl,5-cyclohexyloxy-3-oxapentyl, 6-cyclohexyloxy-4-oxahexyl,8-cyclohexyloxy-4-oxaoctyl, 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl,4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl,5-methoxycarbonyl-3-oxapentyl, 6-methoxycarbonyl-4-oxahexyl,8-methoxycarbonyl-4oxaoctyl, 2-phenoxycarbonylethyl, 2- or3-phenoxycarbonylpropyl, 4-phenoxycarbonylbutyl,5-phenoxycarbonyl-3-oxapentyl, 6-phenoxycarbonyl-4-oxahexyl,8-phenoxycarbonyl-4-oxaoctyl, 2-formyloxyethyl, 2-acetyloxyethyl,2-propionyloxyethyl, 2-butyryloxyethyl, 2-(2-ethylhexanoyloxy)ethyl, 2-or 3-acetyloxypropyl, 2- or 3-propionyloxypropyl, 2- or3-(2-ethylhexanoyloxy)propyl, 4-acetyloxybutyl, 4-propionyloxybutyl,4-(2-ethylhexanoyloxy)butyl, 5-acetyl-oxy-3-oxapentyl,5-propionyloxy-3-oxapentyl, 5-(2-ethyl-hexanoyloxy)-3-oxapentyl,6-acetyloxy-4-oxahexyl, 6-propionyloxy-4-oxahexyl,6-(2-ethylhexanoyloxy)-4-oxahexyl, 8-acetyloxy-4-oxaoctyl,8-propionyloxy-4-oxaoctyl, 8-(2-ethylhexanoyloxy)-4-oxaoctyl,2-benzoyloxyethyl, 2- or 3-benzoyloxypropyl, 4-benzoyloxybutyl,5-benzoyloxy-3-oxapentyl, 6-benzoyloxy-4-oxahexyl,8-benzoyloxy-4-oxaoctyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl,allyl or methallyl.

R², besides the possibilities already mentioned, is for example mono- ordimethylcarbamoyl, mono- or diethylcarbamoyl, mono- ordipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- ordibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, formyl, acetyl, propionyl,butyryl, isobutyryl, pentanoyl, hexanoyl, methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,isobutoxycarbonyl, sec-butoxycarbonyl, 2-methoxyethoxycarbonyl,2-ethoxyethoxycarbonyl, 2-propoxyethoxycarbonyl,2-isopropoxyethoxycarbonyl, 2-butoxyethoxycarbonyl,2-iso-2-isobutoxyethoxycarbonyl or 2-sec-butoxyethoxycarbonyl.

Preference is given to isothiazoleazo dyes of the formula I where

X is phenyl or benzyl, which each may be substituted by methyl, methoxy,ethoxy or chlorine, or is C₁ -C₄ -alkyl,

R¹ is methyl,

R² is hydrogen, cyano, carbamoyl or C₁ -C₄ -alkoxycarbonyl and

Y and R³ are each as defined above.

Of particular importance are dyes of the formula I where

X is phenyl or benzyl, which may each be substituted by methyl, methoxy,ethoxy or chlorine, or is C₁ -C₄ -alkyl,

R¹ is methyl,

R² is cyano,

R³ is C₁ -C₈ -alkyl which may be substituted and/or interrupted by oneor two oxygen atoms or is C₃ -C₆ -alkenyl and

Y is as defined above.

To prepare the isothiazoleazo dyes of the formula I according to theinvention, a conventionally obtainable diazonium compound of amines ofthe formula II ##STR3## where X and Y are each as defined above, can bereacted with a 6-hydroxypyrid-2-one derivative of the formula III##STR4## where R¹, R² and R³ are each as defined above, in aconventional manner. Further details of the preparation may be found inthe examples.

The dyes according to the invention are preferably suitable for dyeingsynthetic fibers, for example polyesters, polyamides, cellulose estersor polyester/cellulose fiber blend fabrics. They are suitable inparticular for dyeing polyester. They produce dyeings in yellow shadesand are notable for good light fastness and good affinity. Some of themare also suitable for transfer printing.

The Examples below, where percentages are by weight unless otherwisestated, are intended to illustrate the invention in more detail.

EXAMPLE 1

5.05 g of 5-amino-4-cyano-3-phenylisothiazole were dissolved in 37.5 mlof a 17:3 V/V mixture of glacial acetic acid and propionic acid whileheating. 10 ml of 85% strength sulfuric acid were added dropwise at from10° to 20° C., followed at from 0° to 5° C. by 4.3 ml ofnitrosylsulfuric acid (11.5% of N₂ O₃). This was followed by 4 hours ofstirring at from 0° to 5° C.

The above-prepared diazonium salt solution was added dropwise at 0° C.to 6.0 g of 1-butyl-3-cyano-6-hydroxy-4-methylpyrid-2-one in 30 ml ofN,N-dimethylformamide, 100 g of ice and 0.5 g of amidosulfuric acid.After 4 hours of stirring at from 0° to 5° C., the reaction mixture wasslowly warmed to room temperature and filtered with suction, and theprecipitate was washed and dried to leave 7.7 g of the dye of theformula ##STR5## which dyes polyester material in fast yellow shades(λmax (CH₂ Cl₂): 427 nm).

EXAMPLE 2

4.8 g of 5-amino-4-bromo-3-methylisothiazole in 20 ml of water and 10 mlof dilute hydrochloric acid were admixed at 10° C. with 1.7 g of sodiumnitrite dissolved in 5 ml of water. After 2 hours of stirring at from10° to 15° C., 150 g of ice and 0.5 g of amidosulfuric acid were added.A solution of 5.8 g of 3-cyano-6-hydroxy-1,4-di-methylpyrid-2-one in 70ml of water, whose pH had been adjusted to 9 with sodium carbonate, wasthen added dropwise at from 0° to 5° C. A workup as in Example 1 left8.3 g of a mixture of the dyes of the formula ##STR6## where Y ischlorine and bromine. The dye mixture dyes polyester in fast yellowshades (λmax(CH₂ Cl₂): 437 nm).

EXAMPLE 3

3.75 g of 5-amino-3-methylisothiazole hydrochloride in 40 ml of water,10 ml of dilute hydrochloric acid and 25 g of ice were admixed with 1.7g of sodium nitrite dissolved in 5 ml of water, and the mixture wassubsequently stirred at from 0° to 5° C. for 2 hours. The couplingreaction which was carried out as described in Example 2, except that6.0 g of 1-butyl-3-cyano-6-hydroxy-4-methyl-pyrid-2-one were used as thecoupling component, gave after a customary workup 6.9 g of the dye ofthe formula ##STR7## which dyes polyester material in fast yellow shades(λmax(CH₂ Cl₂): 432 nm.

The same method was used to obtain the dyes listed in the table below,which dye polyester material in yellow shades.

                                      TABLE                                       __________________________________________________________________________     ##STR8##                                                                     Ex.                                                                           No.                                                                              X         Y  R.sup.1                                                                          R.sup.2                                                                              R.sup.3                                             __________________________________________________________________________     4 C.sub.6 H.sub.5 CH.sub.2                                                                CN CH.sub.3                                                                         CN     CH.sub.3                                             5 C.sub.6 H.sub.5 CH.sub.2                                                                CN CH.sub.3                                                                         CN     C.sub.4 H.sub.9                                      6 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2                                                    CN CH.sub.3                                                                         CN                                                                                    ##STR9##                                            7 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2                                                    CN CH.sub.3                                                                         CN     C.sub.3 H.sub.7                                      8 p-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                     CN CH.sub.3                                                                         CN     CH.sub.3                                             9 p-CH.sub.3 C.sub.6 H.sub.4 CH.sub.2                                                     CN CH.sub.3                                                                         CN     CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9         10 CH.sub. 3 CN CH.sub.3                                                                         CN     C.sub.6 H.sub.13                                    11 CH.sub.3  CN CH.sub.3                                                                         CN     C.sub.3 H.sub.6 OC.sub.6 H.sub.5                    12 CH.sub.3  CN CH.sub.3                                                                         CN     C.sub.2 H.sub.5                                     13 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CN     CH.sub.3                                            14 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CN     C.sub.3 H.sub.7                                     15 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CN                                                                                    ##STR10##                                          16 CH(CH.sub.3).sub.2                                                                      CN CH.sub.3                                                                         CN     C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5                                             17 CH(CH.sub.3).sub.2                                                                      CN CH.sub.3                                                                         CN     C.sub.4 H.sub.9                                     18 p-CH.sub.3 OC.sub.6 H.sub.4                                                             CN CH.sub.3                                                                         CN     CH.sub.3                                            19 p-CH.sub.3 C.sub.6 H.sub.4                                                              CN CH.sub.3                                                                         CN     C.sub.3 H.sub.7                                     20 CH.sub.3  Br CH.sub.3                                                                         CN     C.sub.4 H.sub.9                                     21 CH.sub.3  Br CH.sub.3                                                                         CN     CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9         22 CH.sub.3  Cl CH.sub.3                                                                         CN     CH.sub.3                                            23 CH.sub.3  Cl CH.sub.3                                                                         CN     C.sub.6 H.sub.13                                    24 CH.sub.3  Cl CH.sub.3                                                                         CN     C.sub.4 H.sub.9                                     25 CH.sub.3  H  CH.sub.3                                                                         CN     CH.sub.3                                            26 CH.sub.3  H  CH.sub.3                                                                         CN     C.sub.3 H.sub.7                                     27 CH.sub.3  H  CH.sub.3                                                                         CN                                                                                    ##STR11##                                          28 C.sub.6 H.sub.5                                                                         CN H  CN     CH.sub.3                                            29 CH.sub.3  CN H  CONHC.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                     30 CH.sub.3  Br H  CONHC.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                     31 C.sub.6 H.sub.5 CH.sub.2                                                                CN CH.sub.3                                                                         H      C.sub.2 H.sub.5                                     32 C.sub.3 H.sub.7                                                                         CN CH.sub.3                                                                         H      C.sub.2 H.sub.5                                     33 CH.sub.3  Cl CH.sub.3                                                                         H      C.sub.2 H.sub.5                                     34 CH.sub.3  H  CH.sub.3                                                                         H      C.sub.2 H.sub.5                                     35 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2                                                    CN CH.sub.3                                                                         CONH.sub.2                                                                           CH.sub.3                                            36 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CONH.sub.2                                                                           CH.sub.3                                            37 p-ClC.sub.6 H.sub.4                                                                     CN CH.sub.3                                                                         CONH.sub.2                                                                           CH.sub.3                                            38 CH.sub.3  Br CH.sub.3                                                                         CONH.sub.2                                                                           CH.sub.3                                            39 CH.sub.3  CN CH.sub.3                                                                         CONH.sub.2                                                                           CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9         40 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CO.sub.2 C.sub.2 H.sub.5                                                             C.sub.4 H.sub.9                                     41 CH.sub.3  CN CH.sub.3                                                                         CO.sub.2 C.sub.2 H.sub.5                                                             C.sub.4 H.sub.9                                     42 CH.sub.3  Br CH.sub.3                                                                         CO.sub.2 C.sub.2 H.sub.5                                                             C.sub.4 H.sub.9                                     43 CH.sub.3  Br CH.sub.3                                                                         CN     H                                                   44 C.sub.6 H.sub.5 CH.sub.2                                                                CN CH.sub.3                                                                         CN     H                                                   45 C.sub.6 H.sub.5                                                                         CN CH.sub.3                                                                         CN     CH.sub.2 CHCH.sub.2                                 46 CH.sub.3  CN CH.sub.3                                                                         CN     CH(CH.sub.3).sub.2                                  47 CH.sub.3  Br CH.sub.3                                                                         CN     CH(CH.sub.3).sub.2                                  __________________________________________________________________________

We claim:
 1. An isothiazoleazo of the formula I: ##STR12## where X is aC₁ -C₈ -alkyl, a C₁ -C₈ -alkyl substituted with chlorine, bromine,cyano, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, C₁ -C₄ -alkoxycarbonyl, phenylor phenyl substituted with C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine,bromine or cyano, or X is phenyl or phenyl substituted with C₁ -C₄-alkyl, hydroxyl, C₁ -C₄ -alkoxy, phenoxy, chlorine, bromine, C₁ -C₄-alkoxycarbonyl, cyano or C₁ -C₄ -dialkyIaminosulphonyl,Y is hydrogen,cyano, chlorine or bromine, R¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, R²is hydrogen, cyano, carbamoyl, C₁ -C₄ -monoalkyl- or -dialkyl-carbamoyl,C₁ -C₆ -alkanoyl, C₁ -C₆ -alkoxycarbonyl or 2-(C₁ -C₄-alkoxy)-ethoxycarbonyl and R³ is hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkylsubstituted with phenyl, cyano, C₁ -C₈ -alkoxycarbonyl, phenoxycarbonyl,halogen, hydroxyl, C₁ -C₈ -alkanoyloxy, benzoyloxy, C₅ -C₇ -cycloalkoxyor phenoxy or C₁ -C₈ -alkyl interrupted by one or two oxygen atoms, oris C₅ -C₇ -cycloalkyl, C₃ -C₆ -alkenyl or phenyl.
 2. The isothiazoleazodye as claimed in claim 1, whereinX is phenyl or benzyl, or phenyl orbenzyl substituted with methyl, methoxy, ethoxy or chlorine, or is C₁-C₄ -alkyl, R¹ is methyl, R² is hydrogen, cyano, carbamoyl or C₁ -C₄-alkoxycarbonyl and Y and R³ are each as defined in claim
 1. 3. Theisothiazoleazo dye as claimed in claim 1, whereinX is phenyl or benzyl,or phenyl or benzyl substituted with methyl, methoxy, ethoxy orchlorine, or is C₁ -C₄ -alkyl, R¹ is methyl, R² is cyano, R³ is C₁ -C₈-alkyl or C₁ -C₈ -alkyl substituted or interrupted by one or two oxygenatoms or is C₃ -C⁶ -alkenyl and Y is as defined in claim
 1. 4. A methodof using an isothiazoleazo dye as claimed in claim 1, for dyeingsynthetic fibers.